Imidazole acetals

ABSTRACT

Imidazoles and salts thereof, the imidazoles being N-substituted by alkyl having 12 or 13 carbon atoms, alkoxyalkyl wherein the alkoxy portion has 2-13 carbon atoms and the alkyl portion has 113 carbon atoms, dimethoxy- or diethoxyethyl or unsubstituted or substituted phenoxy-methoxyethyl, and uses in insecticide compositions in admixture with pyrethrins, carbamates or phosphoric esters in the weight ratio of 1:10 to 1:1.

United States atent Adolphi et a1. [4 Aug. 1, 1972 [541 IMIDAZOLE ACETALS FOREIGN PATENTS 0R APPLICATIONS Inventors: Heinrich Adolphi, Limbvrgerhof, 656,675 6/1965 Belgium ..260/309 Upper Palatinate, Anna Steimmig, Ludwigshafen, Rhine; Hermann OTHER PUBLICATIONS Spaenig, Limburgerhof, Upper Palatinate, all of Germany [73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen, Rhine, Pfalz, Germany p [22] Filed: May 28, 1970 [21] Appl. N0.: 41,612

Related U.S. Application Data [62] Division of Ser. No. 563,964, July 11, 1966,

Pat. No. 3,531,494.

[30] Foreign Application Priority Data July 22, 1965 Germany ..B 82,952

[52] U.S. Cl ..260/309, 424/273 [51] Int. Cl. ..C07d 49/36 [58] Field of Search ..260/309 [56] References Cited UNITED STATES PATENTS 2,380,698 7/1945 Jayne et al. ..260/309 2,404,299 7/ 1946 Kyrides ..260/309 2,710,870 6/1955 Lawson ..260/309 3,178,446 4/1965 Sannicolo ..260/209 Roe J. Chem. Soc. (London) 1963, pages 2195- 2200. QDl.C6

Koenig et al. Chem. Abst. Vol. 61, column 5534 (1964) QD1.A51 (Abstract Belgium Patent 630,161) Beilsteins Hanbuch der Organischen Chemie 4th ed. First supplement (1910-1919) volume 23, page 103. Berlin, Sprinoer, 1936 QD251.B4

Burgess et al. Proc. Soc. Exptl. Biol. Med. Vol. 28, pages 115- 116 (1930) QD1.58

Primary Examiner-Natalie Trousof Attorney-Johnston, Root, OKeeffe, Keil, Thompson & Shurtlefi [5 7] ABSTRACT lmidazoles and salts thereof, the imidazoles being N- substituted by alkyl having 12 or 13 carbon atoms, alkoxyalkyl wherein the alkoxy portion has 2-13 carbon atoms and the alkyl portion has 1-13 carbon atoms, dimethoxyor diethoxyethyl or unsubstituted or substituted phenoxy-methoxyethyl, and uses in insecticide compositions in admixture with pyrethrins, carbamates or phosphoric esters in the weight ratio of 1:10 to 1:1.

6 Claims, No Drawings AZOLE ACETALS RELATED APPLICATION This application is a division of our application Ser. No. 563,964, filed July 11, 1966, now US. Pat. No. 3,531,494.

INTRODUCTION slight.

DESCRIPTION or THE INVENTION An object of the invention is to provide new imidazole compounds. The new imidazoles are those having the formula HC=CH in which R denotes alkyl having twelve or thirteen carbon atoms; alkoxyalkyl wherein the alkoxy portion has two to 13 carbon atoms and the alkyl portion has one to thirteen carbon atoms; or the radical dimethylacetal, diethylacetal, phenyhnethylacetal, methylphenylmethylacetal, or chlorophenylmethylacetal. The acetal radicals are 2,2-dirnethoxyethyl, 2,2-diethoxyethyl, 2- phenoxy-2-methoxyethyl, 2-methylphenoxy-2-methoxyethyl and 2-chlorophenoxy-2-methoxyethyl. These imidazoles, or the salts of these compounds, have a marked synergistic action on pyrethrins, carbamates or phosphoric esters. The known insecticidal action of these active ingredients is considerably enhanced by the said imidazole derivatives and/or their salts.

The imidazole derivatives may be prepared by cyclization synthesis of imidazoles by prior art methods, by dehydrogenation of imidazolines or by further conversion of imidazoles, mainly by N-substitution. The N-substitution may be carried out by known methods by reaction of imidazoles or their salts with ethyl halides or esters of oxalic acid or carbonic acid or by reaction with alcohols in contact with watereliminating catalysts. By adding imidazoles on to reactive double bonds, N-substitution products are also formed. The imidazoles may also be modified by methylolation or conversion of functional groups, for example, esterification, conversion of chlorine into amino groups or by salt formation. For example the production of dodecylimidazoly]acetaldehyde-QN- acetal having the formula may be carried out as follows:

318 parts (by weight) of vinyl dodecyl ether, 68 parts of imidazole and 1 part of hydroquinone are heated for 5 hours at 180 C. while stirring.

The reaction mixture is then vacuum distilled. Dodecylimidazolylacetaldehyde-O,N-acetal distills at 171 to 174 C. at 1.7 mm Hg in a yield of 206 parts (iLe. 73.5 percent of the theory).

Insecticides according to this invention may be prepared by mixing the imidazole derivatives with known insecticidal active ingredients. They may also contain conventional solid or liquid carriers and/or other active ingredients.

The salts include salts with inorganic or organic acids, for example hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, trichloroacetic acid, p-toluenesulfonic acid, phenol, cresol and methylsulfuric acid.

Pyrethrins include not only unpurified or purified pyrethrum extracts but also the pyrethrins isolated from these extracts and the synthetic analogues, for ex ample allethrin.

Carbamates include for example thea -naphthyl ester of N-methylcarbamic acid (Carbaryl), isopropoxyphenylmethyl carbamate (propoxur) and dimethylamino-3,5-xylylmethyl carbarnate (Zectran).

Phosphoric esters include for example 0,0- dimethyl-S-( l ,2-di-(ethoxycarbonyl)-ethyl)- phosphorus dithioate (Malathion), 0,0-dimethyl-S- methylcarbamoylmethylphosphorus dithioate (Dimethoate) and 0,0-dimethyl-O-4-bromo-2,5- dichlorophenylphosphorus dithioate (Bromophos).

The imidazole derivatives and the active ingredients may be used in any relative Proportions. We prefer a mixing ratio of imidazole derivative to active ingredient of 10:1 to 1:1 parts by weight.

The following table gives a selection of active compounds with their melting points (mp) or boiling point (hp) at the reduced pressure indicated:

S28 (Mixture) 13. mm. C.

O-CH3 I 3 4 The following known phosphoric acid esters are used for the following experiments:

I C1130 IS Malnthlon.

P-'s-CHCOO-C2m c1130 cnr-coo-oim II 01330 S Dimetlioato.

1 SCHz-CONHCH:

III Cl Bromoplios.

CHsO s IL O --Br 0310 C1 1v c1130 0 CH3 i -o-c=cH-coN 01130 on: CH1

and the following known carbuniates:

V (I)CONH-CH3 Carbaryl.

VI Propoxur.

OCONHCH:

O-CHCH;

v11 CH3 N -0-o O-NHCH; CH3

The following known syncrglsts are used as comparison substances:

VIII O Plperonyl butoxlde.

/ oHrcm-om Uon,o-omomo-om-cm-o-oin.

IX ias-semi;

o -i iocH,-cH,-o-oH,oH,-00.H

S mg M P A-l0% E The action of the above-mentioned substances is illustrated in the following Examples. 50

3 lmg a +P 0.1m; 100 10 1:: 21 EXAMPLEI 28 m2 0 +P 011:: 33 1 mg P 0.1 mg 100 Synergistic eflect on pyrethrins: 55 :8 g i 3% mg 1900 Petri dishes having a diameter of 10 cm are wetted with Bork l g 0 I an acetone solution of the active ingredient so that a acid coating of 0.1 mg of pyrethrin and 1 mg of synergist is g g: fig I: 3-} :5 3% contained in each dish. Fifty granary weevils 2a 0.5 mg P 011 mg 99 (Sitophilus granaria L.) are placed in each of the dishes 0 g 3-2 I; 8-: 8 3? after the solvent has evaporated. The eflect is deterlmidazole {m g P 011 :2 24 mined after sixty minutes and stated percentage mor i ig i s 0 tahty(M)v 100 percent means thatallinsects are dead. am 3 In the following Table S N0. of synergist (as in the lists above); mg amount of synergist used; M per- 65 centage mortality; P pyrethrin; A 10 percent EXAMPLE 2 amount of pyrethrin which gives 10 percent mortality; Syn i ti ti on An h i E effect of the mixture given as percentage mortality.

(Experimental procedure as in Example 1 M Allethrin 0.2 mg 30 Allethrin 0.1 mg 15 S. 3 1 mg +0.1 mg Allethrin 100 S. 3 0.5 mg +0.1 mg Allethrin 88 S. 5 1 mg 0.1 mg Allethrin 97 S. 5 0.5 mg 0.1 mg Allethrin 73 S. 23 1 mg 0.1 mg Allethrin 97 S. 28 1 mg 0.1 mg Allethrin 98 S. 28 0.5 mg 0.1 mg Allethrin 99 S. [X 1 mg 0.1 mg Allethrin 62 S. 1X 0.5 mg 0.1 mg Allenthrinttm 44 S. V111 0.5 mg 0.1 mg Allethrin 45 EXAMPLE 3 In the Table, Mal Malathion; A-32 percent 15 amount of Malathion required to give 32 percent mortality.

S mg M Mal A-32% E 3 1 mg 8 Mal 0.1 mg 90 23 1 mg 10 Mal 0.1 mg 97 V111 1 mg 4 Mal 0.1 mg 12 3 0.4 mg+ 0.02 mg IV 74 3 0.02 mg IV 7 28 0.4 mg+ 0.02 mg IV 55 1X 0.4 mg+ 0.02 mg 1V 1 0.4 mg+ 0.02 mg IV 17 3 0.5 mg+ 0.1 mg 111 43 3 0.1 mg 111 1X 0.5 mg+ 0.1 mg 111 3 V111 0.5 mg+ 0.1 mg 11] 2 EXAMPLE 4 Synergistic efiect on pyrethrins:

Pyrethrin LD 50 0.12 'y/fly Pyr. s. 3 1 1 10 LD 50 0.043 -y/fiy Pyr. s. 28 l 10 LD 50 0.025 ylfly Pyr. s. 33 1 10 LD 50 0.079 'y/fly Pyr. s. 35 1 10 LD 50 0.06 'y/fly By adding the synergists, the amount of pyrethrin required to kill 50% of the flies is substantially decreased. The LD 50 of the pure substances was in all cases more than 10 'y/fly and was therefore not determined more exactly.

EXAMPLE Synergistic effect on carbamates:

Petri dishes having a diameter of cm are wetted with an acetone solution of the active ingredient and houseflies are placed in the dishes after the solvent has evaporated. F our hours later the mortality of the flies is determined.

V 2 mg 0% V l mg+S. 3 1 mg 100% V 0.5 mg-l-S. 3 1 mg 100% S. 3 1 mg 8% V 2mg+S. 28 1 mg 100% V 1 mg+S. 28 l mg 100% V 0.5 mg +S. 28 1 mg 79% V1 0.01 mg 30% V1 0.005 mg S. 28 0.025 mg V11 0.1 mg 48% V11 0.1 mg S. 3 0.05 mg 97% V1] 0.1 mg +3. 3 0 1 mg 94% V11 0.1 mg +8. 3 0 5 mg 98% V11 0.1 mg S. 28 0 05 mg 60% V1] 0.1 mg S. 28 0 5 mg 77% In the above tables, the Roman numerals designate the compounds earlier identified by corresponding Roman numerals.

EXAMPLE 6 Preparation of the compound having the formula 100 parts (by weight) of bromoacetaldehyde diethylacetal is introduced at 50 C. into a solution of 45 parts of sodium imidazole in parts of dimethylfonnamide. The reaction mixture is kept at 50 C. for about 3 hours and then allowed to cool. The precipitated sodium bromide is suction filtered and the filtrate evaporated in vacuo. After the residue has been fractionally distilled, 45 parts of imidazole-N-acetaldehyde diethylacetal is obtained having a boiling point of 1 l0-l 12 C. at 1 mm Hg (49 percent of the theory).

EXAMPLE 7 Preparation of the compound having the formula OCH 65 parts of sodium imidazole is dissolved in 200 parts of dimethylformamide and 90 parts of chloroacetaldehyde dimethylacetal is added. The solution is heated at 80 C. for 8 hours. After cooling, the sodium chloride is suction filtered, the filtrate is evaporated in vacuo and the residue fractionally distilled. 55 parts of imidazole-N-acetaldehyde dimethylacetal with a boiling point of l0l-102 C. at 0.7 mm Hg is obtained. This represents a yield of 49 percent of the theory.

EXAMPLE 8 Preparation of the compound having the formula 136 parts of imidazole is heated for 10 hours at C. I

in an autoclave with 200 parts of vinylethyl ether and 0.1 part of hydroquinone. 250 parts of acetaldehyde ethylimidazolyl-O,N-acetal is obtained from the fraction which boils at 95-97 C. at 8.5 mm Hg (yield 88 percent of the theory).

7 8 The invention is hereby claimedasfollows: 2. An imidazole as claimed in claim 1 wherein R I. An imidazole of the formula denotes 2,2-dimethoxyethyl.

3. An imidazole as claimed in claim 1 wherein R denotes 2,2-diethoxyethyl. N 4. An imidazole as claimed in claim 1 wherein R fi denotes 2-phenoxy-2-methoxyethyl.

- 5. An imidazole as claimed in claim 1 wherein R in which R denotes 2,2-dimethoxyethyl, 2,2-diethoxdenotes Z-methylphenoxy-Z-methoxyethyl.

yethyl, Z-phenoxy-Z-methoxyethyl, Z-methylphenoxy- 6. An imidazole as claimed in claim 1 wherein R Z-methoxyethyl or 2-ch1orophenoxy-Z-methoxyethyl. 10 denotes 2-chiorophenoxy-Z-methoxyethyl. 

2. An imidazole as claimed in claim 1 wherein R1 denotes 2,2-dimethoxyethyl.
 3. An imidazole as claimed in claim 1 wherein R1 denotes 2,2-diethoxyethyl.
 4. An imidazole as claimed in claim 1 wherein R1 denotes 2-phenoxy-2-methoxyethyl.
 5. An imidazole as claimed in claim 1 wherein R1 denotes 2-methylphenoxy-2-methoxyethyl.
 6. An imidazole as claimed in claim 1 wherein R1 denotes 2-chlorophenoxy-2-methoxyethyl. 